Benzoylpenylureas

ABSTRACT

The invention relates to novel substituted N-benzoyl-N&#39;-2,5-dichloro-4-hexafluoropropyloxyphenylureas of the formula ##STR1## wherein R 1  is hydrogen, fluorine, chlorine or methoxy, and R 2  is fluorine, chlorine or methoxy, and to the salts thereof; to processes and intermediates for the preparation of these compounds and to compositions containing the novel compounds for controlling insects and representatives of the order Acarina, in particular plant-destructive insects.

This is a divisional of application Ser. No. 262,121 filed on Oct. 24,1988 now U.S. Pat. No. 4,980,506 which is a divisional of Ser. No.058,631 filed Jun. 4, 1987 now U.S. Pat. No. 4,798,837 which is acontinuation of Ser. No. 786,418 filed Oct. 10, 1985, now abandoned.

The present invention relates to novel substitutedN-benzoyl-N'-2,5-dichloro-4-hexafluoropropyloxyphenylureas, to processesand to intermediates for the preparation thereof, and to the use of thenovel compounds in pest control.

The invention relates to compounds of formula I ##STR2## wherein R₁ ishydrogen, fluorine, chlorine or methoxy and R₂ is fluorine, chlorine ormethoxy, and to salts thereof.

Compounds of formula I meriting particular interest are those wherein R₁is hydrogen, fluorine or chlorine and R₂ is fluorine, chlorine ormethoxy.

Further compounds of formula I meriting particular interest are thosewherein R₁ and R₂ are simultaneously fluorine, chlorine or methoxy.

Still further preferred compounds of formula I are those wherein R₁ ishydrogen, fluorine or chlorine and R₂ is fluorine or chlorine, as wellas those compounds wherein R₁ is hydrogen or fluorine and R₂ is fluorineor chlorine.

The compounds of formula I can be prepared by methods analogous to onesknown per se (q.v. for example German Offenlegungsschrift specifications2 123 236, 2 061 780 and 3 240 975). Thus, for example, a compound offormula I can be obtained by reacting

a) the compound of formula II ##STR3## with a compound of formula III##STR4## or

b) the compound of formula IV ##STR5## with a compound of formula V##STR6## or

c) the compound of formula II with a compound of formula VI ##STR7##

In formulae III, V and VI above, R₁ and R₂ are as defined for formula I,and R is a C₁ -C₈ alkyl radical which is unsubstituted or substituted byhalogen, preferably chlorine.

The above processes a), b) and c) can preferably be carried out undernormal pressure and in the presence of an organic solvent or diluent.Examples of suitable solvents or diluents are: ethers and etherealcompounds, such as diethyl ether, dipropyl ether, dibutyl ether,dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylatedcarboxamides; aliphatic, aromatic and halogenated hydrocarbons,especially benzene, toluene, xylene, chloroform, methylene chloride,carbon tetrachloride and chlorobenzene; nitriles such as acetonitrile orpropionitrile; dimethyl sulfoxide; and ketones, e.g. acetone, methylethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone.Process a) is normally carried out in the temperature range from -10° to+200° C., preferably from 0° to 100° C., e.g. at room temperature, and,if desired in the presence of an organic base, e.g. triethylamine.Process b) is carried out in the temperature range from 0° to 150° C.,preferably at the boiling point of the solvent employed and, if desired,in the presence of an organic base such as pyridine, and/or with theaddition of an alkali metal or alkaline earth metal, preferably sodium.For process c), i.e. for the reaction of the urethane of formula VI withan aniline of formula II, a temperature range from about 60° to theboiling point of the reaction mixture is preferred, and the solventemployed is preferably an aromatic hydrocarbon such as toluene, xylene,chlorobenzene and the like.

The starting materials of formulae III and V are known and can beprepared by methods analogous to known ones. The starting aniline offormula II is a novel compound which likewise constitutes an object ofthe present invention. The compound of formula II can be prepared in amanner known per se by hydrogenating the suitably substitutednitrobenzene of formula VII ##STR8## by a process analogous to thatdescribed in J. Org. Chem. 29 (1964), 1, (q.v. also the literature citedtherein). However, the aniline of formula II can also be obtained bychemical reduction (e.g. with Sn(II) chloride/HCl) of the nitro compoundof formula VII (q.v. Houben-Weyl, "Methoden d. org. Chemie" 11/1, 422).The nitro compound of formula VII itself can be prepared byhaloalkylating 2,5-dichloro-4-nitrophenol. A further process for thepreparation of the aniline of formula II comprises haloalkylating incorresponding manner acylated 2,5-dichloro-4-hydroxyaniline and thenremoving the acyl group, e.g. by acid hydrolysis, or effecting thehaloalkylation with a salt of 2,5-dichloro-4-hydroxyaniline, e.g. thechlorohydrate.

Benzoylisocyanates of formula III can be obtained, inter alia, asfollows (q.v. J. Agr. Food Chem. 21, 348 and 993; 1973): ##STR9## The4-(hexafluoropropyloxy)phenylisocyanate of formula IV (b.p. 95° C./0.01torr), which is novel per se, can be prepared e.g. by phosgenating theaniline of formula II by methods which are commonly employed in the artand also comprises an object of this invention. The benazmides offormula V which are further used as starting materials are known (q.v.for example Beilstein "Handbuch der organischen Chemie", Vol. 9, p.336).

Urethanes of formula VI can be obtained in a manner known per se byreacting a benzoylisocyanate of formula III with a suitable alcohol orby reacting a benzamide of formula V, in the presence of a base, with acorresponding ester of chloroformic acid Cl--COOR.

In accordance with the present invention, the novel compounds of formulaI also comprise the salts thereof which not only exhibit highinsecticidal activity, but are also readily soluble in solvents anddiluents, in particular in organic solvents, and can also be formulatedmore easily.

To be singled out for special mention are the metal salts of thecompounds of formula I of the invention, in particular the alkali metaland alkaline earth metal salts thereof, preferably the sodium salts andpotassium salts. These salts are prepared in a manner known per se, e.g.by reacting a compound of formula I with a metal alkanolate such assodium ethylate or potassium methylate. A given salt can be convertedinto a desired salt of another metal by inter-reaction, e.g. withanother alkanolate.

Of particular importance are the salts of compounds of formula I withorganic bases, an essential feature of which is the presence of aquaternary nitrogen atom. Such salts are of formula Ia ##STR10## whereinR₁ and R₂ are as defined above and X.sup.⊕ is the cation of an organicbase. X.sup.⊕ is preferably one of the following organic cations:##STR11## whereby n is an integer from 8 to 12. The salts of formula Iaalso comprise mixtures of these salts with different cations. The saltsof formula Ia can be prepared in a manner known per se by reacting acompound of formula I with corresponding ammonium hydroxides of theformula X.sup.⊕ (OH).sup.⊖, wherein X.sup.⊕ is as defined above.

Surprisingly, it has been found that the compounds of this invention andthe salts thereof have excellent properties as pesticides while beingwell tolerated by plants and having low toxicity to warm-bloodedanimals. They are particularly suitable for controlling insects andrepresentatives of the order Acarina that attack plants and animals.

In particular, the compounds of formula I are suitable for controllinginsects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera,Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga,Thysanura, Isoptera, Psocoptera and Hymenoptera, as well asrepresentatives of the order Acarina of the families: Ixodidae,Argasidae, Tetranychidae and Dermanyssidae.

In addition to their action against flies, e.g. Musca domestica, andmosquito larvae, the compounds of formula I are also suitable forcontrolling plant-destructive feeding insects in ornamentals and cropsof useful plants, especially in cotton (e.g. against Spodopteralittoralis and Heliothis virescens) and in fruit and vegetables (e.g.against Laspeyresia pomonella, Leptinotarsa decemlineata and Epilachnavarivestis). The compounds of formula I have a pronounced ovicidal and,in particular, larvicidal action against insects, especially againstlarvae of noxious feeding insects. If compounds of formula I areingested by adult insect stages with the feed, then a diminishedoviposition and/or reduced hatching rate is observed in many insects,especially in Coleopterae, e.g. Anthonomus grandis.

The compounds of formula I can also be used for controllingectoparasites such as Lucilia sericata, in domestic animals andproductive livestock, e.g. by treating animals, cowsheds, barns, stablesetc., and pastures.

The compounds of formula I are also suitable for controlling thefollowing species of mites which attack crops of fruit and vegetables:Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Broybiarubrioculus, Panonychus citri, Eriophyes piri, Eriophyes ribis,Eriophyes vitis, Tarsonemus pallidus, Phyllocoptes vitis andPhyllocoptruta oleivora.

The good pesticidal activity of the compounds of formula I of theinvention corresponds to a mortality of at least 50-60% of the abovepests.

The activity of the compounds of formula I and of the compositionscontaining them can be substantially broadened and adapted to prevailingcircumstances by addition of other insecticides and/or acaricides.Examples of suitable additives include: organophosphorus compounds,nitrophenols and derivatives thereof, formamidines, ureas, carbamates,pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensispreparations.

The compounds of formula I are used in unmodified form, or preferablytogether with the adjuvants conventionally employed in the art offormulation, and are therefore formulated in known manner toemulsifiable concentrates, directly sprayable or dilutable solutions,dilute emulsions, wettable powders, soluble powders, dusts, granulates,and also encapsulations in e.g. polymer substances. As with the natureof the compositions, the methods of application such as spraying,atomising, dusting, scattering or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixturescontaining the compound (active ingredient) of the formula I orcombinations thereof with other insecticides or acaricides, and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, in some cases,surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycolmonomethyl or monoethyl ether, ketones such as cyclohexanone, stronglypolar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide ordimethylformamide, as well as vegetable oils or epoxidised vegetableoils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated absorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,or of combinations thereof with other insecticides or acaricides,suitable surface-active compounds are nonionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained, e.g. from coconutoil or tallow oil. Further suitable surfactants are also the fatty acidmethyltaurin salts as well as modified and unmodified phospholipids.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate, or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product. Also suitable are correspondingphosphates, e.g. salts of the phosphoric acid ester of an adduct ofp-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, caster oil polyglcol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylenesorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitablenon-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MCPublishing Corp. Ridgewood, N.J., 1979; Dr. Helmut Stache, "TensidTaschenbuch" (Handbook of Surfactants), Carl Hanser Verlag,Munich/Vienna.

The pesticidal compositions usually contain 0.1 to 99%, preferably 0.1to 95%, of a compound of formula I or combination thereof with otherinsecticides or acaricides, 1 to 99.9% of a solid or liquid adjuvant,and 0 to 25%, preferably 0.1 to 20%, of a surfactant.

Whereas commercial products are preferably formulated as concentrates,the end user will normally employ diluted formulations of substantiallylower concentration.

The compositions may also contain further ingredients, such asstabilisers, antifoams, viscosity regulators, binders, tackifiers aswell as fertilisers or other active ingredients in order to obtainspecial effects.

EXAMPLE 1

a) Preparation of2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)aniline

47 g of 4-acetylamino-2,5-dichlorophenol together with 154 g of 90%potassium hydroxide solution and 130 ml of dimethylformamide are stirredin an autoclave. 75.8 g of hexafluoropropylene are then pressed into theclosed autoclave. The mixture is stirred for 20 hours at 70° C. underthe pressure existing in the autoclave. After cooling, the mixture isconcentrated by rotary evaporation and the residue is dissolved inmethylene chloride. The resultant solution is washed with water, driedover Na₂ SO₄ and concentrated. The crude product obtained as residue ischromatographed through a column of silica gel (length: 1 m; diameter:10 cm) eluted with an 11:1 mixture of toluene and acetone, affording4-acetylamino-2,5-dichloro-1-(1,1,2,3,3,3-hexafluoropropyloxy)benzene inthe form of pale yellow crystals (m.p.: 93°-95° C.), 26 g of which arekept for 10 hours under reflux with 110 ml of ethanol and 35.6 ml of 37%hydrochloric acid. The reaction mixture is then concentrated, dilutedwith ice/water and made weakly alkaline. The product is extracted fromthe mixture with methylene chloride. The organic extract phase is washedwith water, dried over Na₂ SO₄ and concentrated. The residue is purifiedby distillation, thus affording the title compound of the formula##STR12## as a colourless liquid with a boiling point of 81°-83° C./0.05torr.

b) Preparation ofN-(2,6-trifluorobenzoyl)-N'-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl]urea

4.7 g of 2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)aniline aredissolved with stirring in 50 ml of dry toluene and, with exclusion ofmoisture, a solution of 2.62 g of 2,6-difluorobenzoylisocyanate in 10 mlof dry toluene is added at room temperature. The batch is stirred for afurther 10 hours at room temperature. About 75% of the solvent is thenremoved by rotary evaporation, the precipitated residue is filtered withsuction, washed with a small amount of cold toluene and hexane and thendried in vacuo, affording the title compound of the formula ##STR13## inthe form of a crystalline white powder with a melting point of 174°-175°C. (compound 1).

The following compounds of formula I have been prepared in a mannercorresponding to that described above:

    __________________________________________________________________________    Compound                                   m.p.                               __________________________________________________________________________           ##STR14##                           165-166° C.                 3                                                                                    ##STR15##                           188-190° C.                 4                                                                                    ##STR16##                           143-145° C.                 5                                                                                    ##STR17##                           135-137° C.                 6                                                                                    ##STR18##                           176-177° C.                 7                                                                                    ##STR19##                           177-178° C.                 8                                                                                    ##STR20##                           162-163° C.                 9                                                                                    ##STR21##                           190-191° C.                 __________________________________________________________________________

c) Preparation of the sodium salt of compound 1

9.58 g ofN-(2,6-difluorobenzoyl)-N'-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl]ureaare suspended in 20 ml of absolute methanol. A solution of 0.43 g ofsodium in 30 ml of absolute methanol is added dropwise with stirring tothis suspension. A clear solution forms which is then concentrated. Theresidual product is dried in vacuo at room temperature, affording thetitle compound in the form of colourless crystals of the formula##STR22## with a melting point of 169°-171° C. under decomposition(compound 10).

The following salt of compound 2 of the formula below can also beprepared by proceeding as described above:

    __________________________________________________________________________    Compound                                  m.p.                                __________________________________________________________________________    11                                                                                   ##STR23##                          from 140° C./ decompositi                                              on                                  __________________________________________________________________________

d) Preparation of the tetrabutylammonium salt of compound 1

2.56 g ofN-(2,6-difluorobenzoyl)-N'-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropyloxy)phenyl]ureaare suspended in 30 ml of methanol. With stirring, 5.2 g of a methanolicsolution containing 1.3 g of tetra-n-butylammonium hydroxide are addedto this suspension, whereupon a clear solution forms. This solution isconcentrated and the residual crude product is suspended in hexane. Thesuspension is filtered with suction and the filter residue is washedwith hexane and then dried, affording the title compound of the formula##STR24## in the form of colourless crystals with a melting point of110° C. (compound 12).

The following salts of formula Ia can also be prepared in accordancewith this procedure:

    __________________________________________________________________________    Compound                                                                      __________________________________________________________________________    13                                                                                    ##STR25##                                                             14                                                                                    ##STR26##                                                             15                                                                                    ##STR27##                                                             16                                                                                    ##STR28##                                                             17                                                                                    ##STR29##                                                             18                                                                                    ##STR30##                                                             __________________________________________________________________________

EXAMPLE 2 Formulations for active ingredients of formula I according toExample 1 or combinations thereof with other insecticides or acaricides(throughout, percentages are by weight)

    ______________________________________                                        1. Wettable powders   a)      b)      c)                                      ______________________________________                                        compound of formula I or combination                                                                25%     50%     75%                                     sodium lignosulfonate 5%       5%     --                                      sodium laurylsulfate  3%      --       5%                                     sodium diisobutylnaphthalenesulfonate                                                               --       6%     10%                                     octylphenol polyethylene glycol ether                                                               --       2%     --                                      (7-8 moles of ethylene oxide)                                                 highly dispersed silicic acid                                                                       5%      10%     10%                                     kaolin                62%     27%     --                                      ______________________________________                                    

The active ingredient or combination is thoroughly mixed with theadjuvants and the mixture is thoroughly ground in a suitable mill,affording wettable powders which can be diluted with water to givesuspensions of the desired concentration.

    ______________________________________                                        2. Emulsifiable concentrate                                                   ______________________________________                                        compound of formula I or combination                                                                  10%                                                   octylphenol polyethylene glycol ether                                                                  3%                                                   (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate                                                                        3%                                                   castor oil polygycol ether                                                                             4%                                                   (36 moles of ethylene oxide)                                                  cyclohexanone           30%                                                   xylene mixture          50%                                                   ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        3. Dusts                a)     b)                                             ______________________________________                                        compound of formula I or combination                                                                   5%     8%                                            talcum                  95%    --                                             kaolin                  --     92%                                            ______________________________________                                    

Ready for use dusts are obtained by mixing the active ingredient withthe carrier, and grinding the mixture in a suitable mill.

    ______________________________________                                        4. Extruder granulate                                                         ______________________________________                                        compound of formula I or combination                                                                  10%                                                   sodium lignosulfonate    2%                                                   carboxymethylcellulose   1%                                                   kaolin                  87%                                                   ______________________________________                                    

The active ingredient or combination is mixed and ground with theadjuvants, and the mixture is subsequently moistened with water. Themixture is extruded and then dried in a stream of air.

    ______________________________________                                        5. Coated granulate                                                           ______________________________________                                        compound of formula I or combination                                                                  3%                                                    polyethylene glycol 200 3%                                                    kaolin                  94%                                                   ______________________________________                                    

The finely ground active ingredient or combination is uniformly applied,in a mixer, to the kaolin moistened with polyethylene glycol. Non-dustycoated granulates are obtained in this manner.

    ______________________________________                                        6. Suspension concentrate                                                     ______________________________________                                        compound of formula I or combination                                                                  40%                                                   ethylene glycol         10%                                                   nonylphenol polyethylene glycol ether                                                                  6%                                                   (15 moles of ethylene oxide)                                                  sodium lignosulfonate   10%                                                   carboxymethylcellulose   1%                                                   37% aqueous formaldehyde solution                                                                     0.2%                                                  silicone oil in the form of a 75%                                                                     0.8%                                                  aqueous emulsion                                                              water                   32%                                                   ______________________________________                                    

The finely ground active ingredient or combination is intimately mixedwith the adjuvants, giving a suspension concentrate from whichsuspensions of any desired concentration can be obtained by dilutionwith water.

EXAMPLE 3 Action against Musca domestica

50 g of freshly prepared nutrient substrate for maggots are charged intoeach of a number of beakers. A specific amount of a 1% acetonic solutionof the respective test compound is pipetted onto the nutrient substratepresent in the beakers to give an active ingredient concentration of 800ppm. The substrate is then thoroughly mixed and the acetone subsequentlyallowed to evaporate over a period of at least 20 hours.

Then 25 one-day-old maggots Musca domestica are put into each of thebeakers containing the treated nutrient substrate for testing with eachactive ingredient. After the maggots have pupated, the pupae areseparated from the substrate by flushing them out with water and thendeposited in containers closed with a perforated top.

Each batch of flushed out pupae is counted to determine the toxic effectof the test compound on the maggot development. A count is then madeafter 10 days of the number of flies which have hatched out of thepupae.

The compounds of formula I according to Example 1 have good activity inthis test.

EXAMPLE 4 Action against Lucilia sericata

1 ml of an aqueous solution containing 0.5% of test compound is added at50° C. to 9 ml of a culture medium. Then about 30 freshly hatchedLucilia sericata larvae are added to the culture medium, and theinsecticidal action is determined after 48 and 96 hours by evaluatingthe mortality rate.

In this test, compounds of formula I according to Example 1 exhibit goodactivity against Lucilia sericata.

EXAMPLE 5 Action against Aedes aegypti

A concentration of 800 ppm is obtained by pipetting a specific amount ofa 0.1% solution of the test compound in acetone onto the surface of 150ml of water in a beaker. After the acetone has evaporated, 30 to 40two-day-old larvae of Aedes aegypti are put into the beaker containingthe test compound. Mortality counts are made after 1, 2 and 5 days.

In this test, compounds of formula I according to Example 1 exhibit goodactivity against Aedes aegypti.

EXAMPLE 6 Insecticidal action against feeding insects

Cotton plants about 25 cm high, in pots, are sprayed with aqueousemulsions which contain the respective test compound in concentrationsof 0.75, 12,5 and 100 ppm. After the spray coating has dried, the cottonplants are populated with Spodoptera littoralis and Heliothis virescenslarvae in the L₃ -stage. The test is carried out at 24° C. and 60%relative humidity. The percentage mortality of the test insects isdetermined after 120 hours.

Compound 1 according to Example 1 effects 80 to 100% mortality againstSpodoptera larvae and Heliothis larvae at 0.75 ppm. Compound 3 effects80 to 100% mortality against Spodoptera larvae at 12.5 ppm and againstHeliothis larvae at 100 ppm.

EXAMPLE 7 Action against Epilachna varivestis

Phaseolus vulgaris plants (dwarf beans) about 15-20 cm in height aresprayed with aqueous emulsion formulations of the test compound in aconcentration of 800 ppm. After the spray coating has dried, each plantis populated with 5 larvae of Epilachna varivestis (Mexican bean beetle)in the L₄ -stage. A plastic cylinder is slipped over the treated plantsand covered with a copper gauze top. The test is carried out at 28° C.and 60% relative humidity. The percentage mortality is determined after2 and 3 days. Evaluation of feeding damage (anti-feeding effect), and ofinhibition of development and shedding, is made by observing the testinsects for a further 3 days.

The compounds of formula I according to Example 1 exhibit good activityin this test.

EXAMPLE 8 Ovicidal action against Heliothis virescens

Corresponding amounts of a wettable powder formulation containing 25% byweight of the test compound are mixed with sufficient water to producean aqueous emulsion with an active ingredient concentration of 800 ppm.One-day-old egg deposits of Heliothis on cellophane are immersed inthese emulsions for 3 minutes and then collected by suction on roundfilters. The treated deposits are placed in petri dishes and kept in thedark. The hatching rate in comparison with untreated controls isdetermined after 6 to 8 days.

The compounds of formula I according to Example 1 exhibit good activityin this test.

EXAMPLE 9 Action against Laspeyresia pomonella (eggs)

Egg deposits of Laspeyresia pomonella not more than 24 hours old areimmersed on filter paper for 1 minute in an aqueous acetonic solutioncontaining 800 ppm of the test compound.

After the solution has dried, the eggs are placed in petri dishes andkept at a temperature of 28° C. The percentage of larvae hatched fromthe treated eggs and the percentage mortality is evaluated after 6 days.

The compounds of formula I according to Example 1 exhibit good activityin this test.

EXAMPLE 10 Influence on the reproduction of Anthonomous grandis

Anthonomous grandis adults which are not more than 24 hours old afterhatching are transferred in groups of 25 to barred cages. The cages arethen immersed for 5 to 10 seconds in an acetonic solution containing 400pm of the test compound. After the beetles have dried, they are placedin covered dishes containing feed and left for copulation andoviposition. Egg deposits are flushed out with running water twice tothree times weekly, counted, disinfected by putting them for 2 to 3hours into an aqueous disinfectant, and then placed in dishes containinga suitable larval feed. A count is made after 7 days to determine thepercentage mortality of the eggs, i.e. the number of larvae which havedeveloped from the eggs.

The duration of the reproduction inhibiting effect of the test compoundsis determined by monitoring the egg deposits further, i.e. over a periodof about 4 weeks. Evaluation is made by assessing the reduction in thenumber of deposited eggs and hatched larvae in comparison with untreatedcontrols.

Compounds 1 and 3 according to Example 1 exhibit an 80 to 100% ovicidalactivity in this test.

EXAMPLE 11 Action against Anthonomus grandis (adults)

Two cotton plants in the 6-leaf stage, in pots, are each sprayed with awettable aqueous emulsion formulation containing 400 ppm of the testcompound. After the spray coating has dried (about 11/2 hours), eachplant is populated with 10 adult beetles (Anthonomus grandis).

Plastic cylinders, covered at the top with gauze, are then slipped overthe treated plants populated with the test insects to prevent thebeetles from migrating from the plants. The treated plants are then keptat 25° C. and about 60% relative humidity. Evaluation is made after 2,3, 4 and 5 days to determine the percentage mortality of the beetles(percentage in dorsal position) as well as the anti-feeding action ascompared with untreated controls.

Compounds of formula I according to Example 1 exhibit good activity inthis test.

What is claimed is:
 1. The compound of formula IV ##STR31##